Process for producing vinyl polymer having functional group at end and vinyl polymer having functional group at end

ABSTRACT

The objective of the present invention is to provide a production method by which a polymer of a functional group-terminated vinyl monomer can be easily and practically produced. 
     Further, it is another object of the present invention to provide a functional group-terminated vinyl polymer which is useful as a material for the production of various functional products. 
     The first aspect of the present invention is concerned with a production method of a functional group-terminated vinyl polymer comprising a step of synthesizing a halogen atom-terminated vinyl polymer by the radical polymerization reaction of a vinyl monomer in the presence of a halogen compound and a step of introducing a functional group to a terminus by substituting a functional group-containing group for the terminal halogen atom of said vinyl polymer.

TECHNICAL FIELD

The present invention relates to a production method of functionalgroup-terminated vinyl polymers and functional group-terminated vinylpolymers as obtainable by the above method.

BACKGROUND ART

It is known that functional group-terminated polymers may undergocrosslinking, either by themselves or in the presence of another polymerhaving a terminal or chain-interrupting functional group and anappropriate curing agent depending on the properties of functionalgroups, to give functional products having outstanding heat resistance,water resistance, durability, compatibility and other characteristics.Moreover, when a polymer has functional groups at all its moleculartermini, a chain extension by terminus-terminus crosslinking occurs withgood efficiency to give a linear or network high molecular weightpolymer and, hence, a resin with excellent elongation and tensilestrength characteristics.

Functional group-terminated polymers are of great use as, for example,reactive raw materials for resins such as polyester resin, polyurethaneresin, polycarbonate resin, etc., paints, adhesives, self-adhesives,sealants, urethane foams, gel coatings, thermoplastic elastomers,molding compounds, resin modifiers, dampers, elastic wall and floorpanels, textile processing agents, UV.EV-curable resin, high-solidpaints and so forth. These are also useful as various resin additivesand raw materials.

Referring to rubber type polymers among functional group-terminatedpolymers, many reports are available on their syntheses until now.Moreover, polymers having a functional group at both termini of apolyether backbone chain have heretofore been used as starting materialsfor urethane adhesives and sealants or modifiers for epoxy adhesives. Inaddition, polyester resins such as polyethylene terephthalate andpolycaprolactone have also been used in many applications. However, asto other resins, particularly those of vinyl monomers having polargroups, the production method for functional group-terminated vinylpolymers has not been implemented on a commercial scale as yet.

As for a production method of polymers of such functionalgroup-terminated highly polar vinyl monomers, for example, JapaneseKokai Publication Hei-5-255415 discloses a process for synthesizing a(meth)acrylic polymer having an alkenyl group at either terminus byusing an alkenyl group-containing disulfide as a chain transfer agent.Japanese Kokai Publication Hei-5-262808 discloses a process comprisingsynthesizing an acrylic polymer having a hydroxyl group at eitherterminus by using a hydroxyl group-containing disulfide and utilizingthese terminal hydroxyl groups, synthesizing an alkenyl group-terminated(meth)acrylic polymer. However, in the former process, a functionalgroup can hardly be introduced into the terminus with certainty and thelatter process requires a chain transfer agent in a large amount forsynthesizing a hydroxyl group-containing polymer. Thus, these synthetictechnologies have drawbacks in some process parameters or others.

Recently much research has been undertaken on the polymerization by theliving polymerization method inclusive of living ionic polymerizationand living radical polymerization. In the synthesis of polymers by thesepolymerization techniques, the molecular weight and molecular weightdistribution can be controlled and, moreover, by converting the activegroup at the living terminus to a desired substituent group, afunctional group-terminated polymer can be obtainable with comparativeease.

Referring to the production method of a functional group-terminatedpolymer by utilizing the above-mentioned living ionic polymerizationmethod, Japanese Kohyo Publication Hei-4-501883, for instance, disclosesa process for synthesizing a hydroxyl group-terminated poly(meth)acrylicester and a process for synthesizing a (meth)acrylic acid macromonomerby way of living anionic polymerization. However, in the case of suchanionic polymerization, the termination reaction and chain transferreaction cannot be controlled unless anhydrous or low-temperatureconditions are maintained and the reaction does not proceed in theliving fashion so that the terminal transformation is renderedimpossible. Therefore, the technology is lacking in commercial utility.

Referring to living radical polymerization, Japanese Kokai PublicationHei-9-272714, for instance, discloses a production method of an alkenylgroup-terminated (meth)acrylic polymer which comprises using anorganohalogen or brominated sulfonyl compound as an initiator and anequivalent amount thereto of a complex of a Group 8 to 11 transitionmetal as a catalyst. However, the transition metal complex has such ahigh affinity for oxygen that unless in a completely inert system itscatalytic activity is lost to arrest the progress of polymerization.Therefore, the technology is not practically useful as for a production.

SUMMARY OF THE INVENTION

The present invention, developed in light of the above state of the art,has for its object to provide a production method by which a polymer ofa functional group-terminated vinyl monomer can be easily andpractically produced.

It is another object of the present invention to provide a functionalgroup-terminated vinyl polymer which is useful as a material for theproduction of various functional products.

The first aspect of the present invention is concerned with a productionmethod of a functional group-terminated vinyl polymer comprising

a step of synthesizing a halogen atom-terminated vinyl polymer by theradical polymerization reaction of a vinyl monomer in the presence of ahalogen compound and

a step of introducing a functional group to a terminus by substituting afunctional group-containing-group for the terminal halogen atom of saidvinyl polymer,

said halogen compound having a structure such that said halogen atom isbound to a carbon atom linked to an aromatic ring and

said radical polymerization reaction being carried out either by lightirradiation or light irradiation in the presence of a Group 14 to 16metal compound or by heating in the presence of a Group 14 to 16 metalcompound.

The second aspect of the present invention is concerned with aproduction method of a functional group-terminated vinyl polymercomprising

a step of synthesizing an iodine atom-terminated vinyl polymer by theradical polymerization reaction of a vinyl monomer in the presence of aniodine compound and

a step of introducing a functional group to the terminus by substitutinga functional group-containing group for the terminal iodine atom of saidvinyl polymer,

said iodine compound having a structure such that said iodine atom isbound to a carbon atom linked to an aromatic ring and

said radical polymerization reaction being carried out either by heatingor by heating in the presence of a radical polymerization initiator.

The third aspect of the present invention is concerned with a functionalgroup-terminated vinyl polymer as obtainable by the production methodaccording to the first aspect or the second aspect of the invention

which has a number average molecular weight of 500 to 50,000 and aterminal functional group introduction rate of not less than 90%.

DISCLOSURE OF THE INVENTION

In the following, the present invention is now described in detail.

In the production method according to the first aspect of the invention,a vinyl monomer is subjected to radical polymerization reaction in thepresence of a halogen compound in the first place to synthesize ahalogen atom-terminated vinyl polymer.

The vinyl monomer to be used in this first aspect of the invention isnot particularly restricted but includes, for example, (meth)acrylicacid, (meth)acrylic esters, styrene derivatives, (meth)acrylonitrile,(meth)acrylamide, vinyl halides, vinyl esters, (meth)acrolein, maleicacid derivatives, fumaric acid derivatives, and so forth. The preferred,among these vinyl monomers, are (meth)acrylic esters, styrenederivatives, (meth)acrylonitrile and vinyl esters. Particularlypreferred are (meth)acrylic esters, styrene derivatives and(meth)acrylonitrile. These vinyl monomers can be used each independentlyor in a combination of two or more species.

The (meth)acrylic esters mentioned above are not particularly restrictedbut include, for example, methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate,pentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate,n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl(meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl(meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,3-methoxypropyl (meth)acrylate, and so forth. These (meth)acrylic estersmay have substituent groups on alkyl chains where necessary.Incidentally, the term (meth)acrylic acid means methacrylic acid oracrylic acid.

The styrene derivatives mentioned above are not particularly restrictedbut include, for example, α-methylstyrene, p-mehtoxystyrene,p-phenoxystyrene, p-t-butoxystyrene, m-methoxystyrene, o-methoxystyrene,p-methylstyrene, p-phenylstyrene, p-chloromethylstyrene,p-t-butylstyrene, m-methylstyrene, p-trimethylsiloxystyrene,o-chlorostyrene, and so forth.

The vinyl esters mentioned above are not particularly restricted butinclude, for example, vinyl acetate, vinyl formate, vinyl propionate,vinyl butyrate, vinyl n-caproate, vinyl isocaproate, vinyl octanoate,vinyl laurate, vinyl palmitate, vinyl stearate, vinyl trimethyl acetate,vinyl chloroacetate, vinyl trichloroacetate, vinyl trifluoroacetate,vinyl benzoate, and so forth.

These vinyl monomers can be used each independently or in a combinationof two or more species.

The form of copolymer as obtainable by using two or more species of saidvinyl monomer is not particularly restricted but includes a randomcopolymer and a block copolymer, for instance. The production methodthereof is not particularly restricted, either. Thus, when a blockcopolymer, for instance, is to be produced, monomers are added into thereaction system serially one after consumption of another.

The halogen compound for use in the production method according to thefirst aspect of the invention has a structure such that a halogen atomis bound to a carbon atom linked to an aromatic ring.

Since, in a halogen compound having the above structure, the halogenatom is bound to a carbon atom linked to an aromatic ring which is anelectron-donating group, the carbon-halogen bond is apt to undergoradical dissociation. Moreover, after the radical dissociation hasoccurred, the radical-stabilizing effect of the aromatic ring πelectrons leads to a higher selective chain transfer activity of thegenerated carbon radical to the vinyl monomer and facilitates reactioncontrol. Therefore, by using a halogen compound having the abovestructure, a halogen atom-terminated vinyl polymer can be easilyobtained.

The halogen compound mentioned above has a structure such that a halogenatom is further bound to a carbon atom directly linked to an aromaticring. The above halogen atom is preferably an iodine atom, a chlorineatom or a bromine atom.

The aromatic ring mentioned above is not particularly restricted butincludes, for example, a benzene ring, a naphthalene ring, an anthracenering, and so forth.

The above aromatic ring may have one or more substituent groups wherenecessary. The above substituent group is not particularly restrictedunless the radical polymerization reaction is there by interfered with,thus including, for example, alkyl, alkoxy, amino, hydroxyl, halogen,carbonyl, carboxyl, mercapto and the like groups. These substituentgroups may have been introduced one species only or two or more species.

To the carbon atom linked to said halogen atom and aromatic ring, one ortwo substituent groups may be linked where necessary. The substituentgroups mentioned above are not particularly restricted insofar as theradical polymerization reaction will not be interfered with, thusincluding, for example, alkyl, alkoxy, amino, hydroxyl, carbonyl,carboxyl, mercapto, and the like groups. These substituent groups may bethe one or two or more species.

Specifically, such halogen compound includes, for example, iodinecompounds such as iodomethylbenzene, iodomethylnaphthalene,1,3-bis(iodomethyl)benzene, 1,4-bis(iodomethyl)benzene,1,3,5-tris(iodomethyl)benzene, diphenyldiiodomethane,4,4′-bis(iodomethyl)biphenyl, bis(4-iodomethylphenyl)methane,4,4′-bis(iodomethyl)diphenyl ether, 1,5-bis(iodomethyl)naphthalene,2,6-bis(iodomethyl) naphthalene,2,4,6,8-tetrakis(iodomethyl)naphthalene, 2,6-bis(iodomethyl)anthracene,9,10-bis(iodomethyl)anthracene, 1,4,5,8-tetrakis(iodomethyl)anthracene,etc.; chlorine compounds such as chloromethylbenzene,chloromethylnaphthalene, 1,3-bis(chloromethyl)benzene,1,4-bis(chloromethyl)benzene, 1,3,5-tris(chloromethyl)benzene,diphenyldichloromethane, 4,4′-bis(chloromethyl)biphenyl,bis(4-chloromethyl-phenyl)methane, 4,4′-bis(chloromethyl)diphenyl ether,1,5-bis(chloromethyl)naphthalene, 2,6-bis(chloromethyl)naphthalene,2,4,6,8-tetrakis(chloromethyl)naphthalene,2,6-bis(chloromethyl)anthracene, 9,10-bis(chloromethyl)anthracene,1,4,5,8-tetrakis(chloromethyl)anthracene, etc.; and bromine compoundssuch as bromomethylbenzene, bromomethylnaphthalene,1,3-bis(bromomethyl)benzene, 1,4-bis(bromomethyl-)benzene,1,3,5-tris(bromomethyl)benzene, diphenyldibromomethane,4,4′-bis(bromomethyl)biphenyl, bis(4-bromomethylphenyl)methane,4,4′-bis(bromomethyl)diphenylether, 1,5-bis(bromomethyl)naphthalene,2,6-bis(bromomethyl)naphthalene,2,4,6,8-tetrakis(bromomethyl)naphthalene,2,6-bis(bromomethyl)anthracene, 9,10-bis(bromomethyl)anthracene,1,4,5,8-tetrakis(bromomethyl)anthracene, and so forth. Among these,iodine compounds are preferred in view of their higher reactivity andchlorine compounds are preferred from availability points of view. Thesehalogen compounds can be used each independently or in a combination oftwo or more species.

Among these halogen compounds, for the purpose of obtaining a linearpolymer having a functional group only at one terminus, a halogencompound having one halogen atom within the molecule is preferred. Forthe purpose of obtaining a linear polymer having a functional group atboth termini, a halogen compound having two halogen atoms within themolecule is preferred. Further, for the purpose of obtaining a stellatepolymer, a halogen compound having three or more halogen atoms withinthe molecule is preferred.

The halogen compound for use in the production method according to thefirst aspect of the invention is preferably a halogen compound havingtwo or more halogen atoms within the molecule, more preferably a halogencompound having two halogen atoms within the molecule. By using saidhalogen compound having two halogen atoms within the molecule, a polymerhaving a halogen atom at both termini of the molecule can bepolymerized, and by substituting a functional group for it, a linearpolymer having the functional group at both termini is obtainable. Then,by using it as the main raw material, a molecular mass increase by chainextension can be efficiently carried out.

In case said halogen compound has two or more halogen atoms within themolecule, the halogen atoms within the molecule may all be of the samespecies or of different species. However, since the reactivity variesaccording to different halogen atom species, they are preferably of thesame species from the standpoint of the ease of reaction control.

For synthesizing said halogen atom-terminated vinyl polymer in theproduction method according to the first aspect of the invention, thevinyl monomer described above is subjected to radical polymerization inthe presence of said halogen compound.

In the production method according to the first aspect of the invention,said radical polymerization is effected either by light irradiation, bylight irradiation in the presence of a Group 14 to 16 metal compound, orby heating in the presence of a Group 14 to 16 metal compound.

Among these, the method involving light irradiation is preferred. Bylight irradiation, the carbon-halogen bond is selectively encouraged toundergo radical dissociation so that chances for side reactions duringpolymerization are diminished.

The light source which can be used for the above light irradiation inthe production method according to the first aspect of the invention isnot particularly restricted insofar as bonds other than thecarbon-halogen bond, e.g. the carbon-carbon bond or carbon-hydrogen bondof the backbone chain, are not cleaved, and can be selected inconsideration of the range of carbon-halogen activation. The above lightsource, for example, includes a high-pressure mercury vapor lamp, alow-pressure mercury vapor lamp, an ultra-high-pressure mercury vaporlamp, a xenon-mercury lamp, an excimer laser, a xenon lamp, and soforth.

The irradiation intensity of said light source is selected within therange not adversely affecting the polymer synthesis and is preferably0.01 to 10J/cm². If the irradiation intensity is less than 0.01 J/cm²,it will not effectively act on the carbon-halogen bond so that thepolymerization reaction tends to be retarded. If the irradiationintensity exceeds 10 J/cm², the reaction may hardly be controlled sincethe irradiation intensity is too high.

In the above method involving light irradiation, a photosensitizer, suchas an azo compound, aperoxide, a carbonyl compound, a sulfur compound oxa dye, a metal compound and/or a radical polymerization initiator may beadded where necessary. These may be used each independently or in acombination of two or more species.

In the first aspect of the invention, when the radical polymerizationreaction by light irradiation is carried out as mentioned above, thelight irradiation is preferably carried out in the presence of a Group14 to 16 metal compound. By using the above Group 14 to 16 metalcompound, the radical dissociation of the carbon-halogen is even morefacilitated to increase the polymerization rate so that thepolymerization period is curtailed and the degree of polymerization isincreased. Moreover, since a Group 14 to 16 metal compound acts as acatalyst, as mentioned hereinafter, for the chemical transformation of ahalogen atom of a polymerization terminus to a functional group, too, itis unnecessary to add a catalyst in the step of chemical transformationof a functional group.

The preferred Group 14 to 16 metal compound is a compound of tin, lead,antimony, bismuth, tellurium and polonium. When said halogen compound isan iodine compound, a compound of tin or bismuth is preferred and whenthe halogen compound is a chlorine compound, a compound of bismuth ispreferred.

The Group 14 to 16 metal compound is not particularly restricted but maybe whichever of an inorganic metal compound or an organic metalcompound. Thus, for example, there can be mentioned tin compounds suchas tin, fluoride, tin chloride, tin bromide, tin iodide, tin oxide, tinbis (2-ethylhexanoate), tin bis(neodecanoate), tinn-butyltris(2-ethylhexanoate), tin acetate,di-n-butylbis(dodecylthio)tin, tin di-n-butylbis(2-ethylhexanoate),di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, di-n-butylmethoxytin,tin, di-n-butyl-S,S′-bis(isooctylmercaptoacetate), tindimethyldineodecanoate, tin dioctyldilaurate, tin dioctyldineodecanoate,tetra-t-butoxytin, tetra-n-butyltin, tetraethyltin, tetraisopropyltin,tetra-n-octyltin, tetra-n-pentyltin, tetraphenyltin, tetra-p-tolyltin,tri-n-butylethoxytin, tri-n-butylmethoxytin, tri-n-butylmethyltin,tri-n-butyltin, etc.; lead compounds such as lead fluoride, leadchloride, lead bromide, lead iodide, lead tetracetate, leadbis(2-ethylhexanoate), lead bis(2,4-pentanedionate), tetraphenyllead,etc.; tellurium compounds such as tellurium ethoxide etc.; andbismuthcompounds such as bismuth chloride, bismuthtris(tetramethylheptanedionate), bismuth tris(t-pentoxide), bismuthtris(2-ethylhexanoate), and so forth. These Group 14 to 16 metalcompounds may be used each independently or in a combination of two ormore species.

The level of addition of said Group 14 to 16 metal compound depends onthe kind of metal compound but is preferably 0.001 to 10 moles per moleof the halogen compound. If the level of the addition of the Group 14 to16 metal compound is below 0.001 mole per mole of the halogen compound,a sufficient catalytic effect may not be obtained. If it exceeds 10moles, the metal compound may not be easily removed in the purificationstep. The more preferred level is 0.05 to 1 mole per mole of the halogencompound.

In the production method according to the first aspect of the invention,the radical polymerization reaction is carried out by heating in thepresence of a Group 14 to 16 metal compound. In the case the halogencompound is not an iodine compound, the radical polymerization reactionmay not proceed well on mere heating. However, heating and using saidGroup 14 to 16 metal compound leads to an increased polymerization rate.In this case, a radical polymerization initiator may be usedconcomitantly.

When the polymerization is carried out by heating and using said Group14 to 16 metal compound, the level of addition of the Group 14 to 16metal compound is preferably the same level as the level used for theabove-described method involving light irradiation.

In the production method according to the first aspect of the invention,the specific method for synthesizing a halogen atom-terminated vinylpolymer by the above radical polymerization is not particularlyrestricted but the hitherto-known polymerization methods can beutilized. For example, the block polymerization method or the solutionpolymerization method can be employed.

When, among these polymerization techniques, the solution polymerizationis used, it is preferred to use a solvent which does not interfere withradical polymerization as a polymerization solvent. As suchpolymerization solvents, there can be mentioned, for example, estersolvents such as ethyl acetate, propyl acetate, butyl acetate, etc.;ketone solvents such as methyl ethyl ketone, cyclohexarone, etc.;aromatic solvents such as benzene, toluene, xylene, etc.; Cellosolvesolvents such as methyl-Cellosolve, ethyl-Cellosolve, etc.;dimethylformamide; dimethyl sulfoxide; and so forth. Thesepolymerization solvents may be used each independently or in acombination of two or more species.

The reaction temperature for use in synthesizing the above halogenatom-terminated vinyl polymer is not particularly restricted but theordinary reaction temperature can be properly selected in accordancewith the kind of vinyl monomer used.

In the production method according to the first aspect of the invention,the synthesis of a halogen atom-containing vinyl polymer is followed bysubstitution of a functional group-containing group for the terminalhalogen atom of said vinyl polymer to thereby introduce the functionalgroup into the terminus.

The functional group to be introduced into the terminus of said vinylpolymer is not particularly restricted unless it is lost with time, thusincluding, for example, hydroxyl, amino, carboxyl, epoxy, vinyl, silyl,ethynyl, mercapto, oxazoline, maleimido, azlactone, and the like groups.Among these, the preferred functional group to be introduced into theterminus is at least one kind of functional group selected from thegroup consisting of hydroxyl, amino, carboxyl, vinyl and silyl groups.The silyl group mentioned above includes hydrosilyl, hydroxysilyl andalkoxysilyl groups.

The method of introducing a functional group into the terminus of saidvinyl polymer is not particularly restricted but the hitherto-knownchemical reactions can be utilized unless the methods cause resindegradation.

The compound (terminal modifier) to be used in the introduction of afunctional group into a terminus of the above vinyl polymer is notparticularly restricted, either, but includes the hitherto-knowncompounds.

The method of introducing a functional group into the terminus of theabove vinyl polymer includes, for example, the introduction of ahydroxyl group by the direct substitution of the terminal halogen withsodium hydroxide or the like; the introduction of a hydroxyl, amino,carboxyl, vinyl or alkoxysilyl group using aminoethanol,ethylenediamine, glycine, p-aminostyrene, or3-aminopropyltriethoxysilane, for instance, in a halogen-aminosubstitution reaction; the introduction of a hydroxyl, carboxyl oralkoxysilyl group using mercaptoethanol, mercaptopropionic acid or3-mercaptopropyltrimethoxysilane, for instance, in a halogen-mercaptosubstitution reaction; the introduction of a carboxyl group through thesubstitution reaction of the terminal halogen with chlorosulfonic acidand subsequent hydrolysis; the introduction of a vinyl group by a ligandinterchange reaction using a vinyl group-containing various organometalcompound; and the introduction of a hydrosilyl group through theaddition of 1,3,5,7,9-pentamethylcyclopentasiloxane to the vinyl groupterminus.

The second aspect of the present invention is concerned with aproduction method of a functional group-terminated vinyl polymercomprising a step of synthesizing an iodine atom-terminated vinylpolymer by the radical polymerization reaction of a vinyl monomer in thepresence of an iodine compound and a step of introducing a functionalgroup to the terminus by substituting a functional group-containinggroup for the terminal iodine atom of said vinyl polymer, said iodinecompound having a structure such that said iodine atom is bound to acarbon atom linked to an aromatic ring and said radical polymerizationreaction being carried out either by heating or by heating in thepresence of a radical polymerization initiator.

The iodine compound for use in the production method according to thesecond aspect of the invention includes the same ones as the iodinecompound for use in accordance with the first aspect of the invention.

Particularly, the iodine compound for use in this production methodaccording to the second aspect of the invention is preferably an iodinecompound having two or more iodine atoms within the molecule, morepreferably an iodine compound having two iodine atoms within themolecule. By using said iodine compound having two iodine atoms withinthe molecule, a polymer having an iodine atom at both termini can bepolymerized, and by substituting a functional group for it, a linearpolymer having the functional group at both termini is obtainable. Then,by using it as a main raw material, a molecular mass increase by chainextension can be efficiently carried out.

In the production method according to the second aspect of the inventionwhere an iodine compound such as described above is used in the step ofpolymerizing a vinyl polymer, the radical polymerization reaction can becarried out by mere heating.

In the second aspect of the invention, when the radical polymerizationreaction is carried out by heating, it is preferred to use a radicalpolymerization initiator, further. The use of a radical polymerizationinitiator leads to increase the polymerization rate so that thepolymerization period is curtailed and the degree of polymerization isincreased.

As said radical polymerization initiator, a compound which generates aradical with heat, light, radiation or a redox chemical reaction can beemployed.

Such radical polymerization initiator is not particularly restricted butincludes, for example, organic peroxides such as dialkyl peroxides,diacyl peroxides and peroxy esters, e.g. peroxycarbonates, ketoneperoxides, peroxyketals, hydroperoxides, lauroyl peroxide, benzoylperoxide, etc.; azo compounds such as 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate,etc.; inorganic peroxides such as potassium persulfate, ammoniumpersulfate, etc.; and redox initiators such as the hydrogenperoxide-iron (II) system, benzoyl peroxide-dimethylaniline system,cerium (IV) salt-alcohol system, and so forth.

These radical polymerization initiators can be properly selected inaccordance with the polymerization conditions such as the polymerizationtemperature and the like. Moreover, these may be used each independentlyor in a combination of two or more species.

The level of said radical polymerization initiator is not particularlyrestricted insofar as it is sufficient to initiate the polymerizationbut is preferably 0.02 to 20 moles per mole of said iodine compound. Ifit is less than 0.02 moles, the polymerization rate will be low and thedegree of polymerization may also be decreased. If it exceeds 20 moles,it may become difficult to control the polymerization reaction. Morepreferably, it is 0.05 to 10 moles per mole of said iodine compound.

In the production method according to the second aspect of theinvention, the other constitutions are identical with those in the firstaspect of the invention.

By using the production method of a functional group-terminated vinylpolymer in accordance with the first or the second aspect of theinvention, a functional group-terminated vinyl polymer can be producedwith ease and commercial advantage.

A third aspect of the present invention is concerned with a functionalgroup-terminated vinyl polymer as obtainable by the production methodaccording to the first or the second aspect of the invention.

The functional group-terminated vinyl polymer according to the thirdaspect of the invention has a number average molecular weight of 500 to50,000 and a terminal functional group introduction rate of not lessthan 90%. If the above number average molecular weight is less than 500,a large amount of a crosslinking agent is required to use it as a rawmaterial for functional products and it is not practical. If the abovenumber average molecular weight exceeds 50,000, when using it as a rawmaterial for functional products, the crosslinking reactivity will bedecreased so that the desired characteristics may not be imparted to thefunctional products to be produced.

Further, if the above terminal functional group introduction rate isless than 90%, in the application of the functional group-terminatedvinyl polymer as a raw material for functional products, no sufficientcrosslinking reaction will take place so that, the desiredcharacteristics may not be imparted to the functional products to beproduced.

The above terminal functional group introduction rate means thepercentage of the number of functional groups actually introduced intothe termini of the vinyl polymer obtainable by the production methodaccording to the first or the second aspect of the invention relative tothe theoretical number of functional groups introduced into the terminiof the vinyl polymer. The number of functional groups actuallyintroduced into the termini of said vinyl polymer can be calculated byusing the hitherto-known determination method.

Such functional group-terminated vinyl polymer can be used withadvantage as a raw material for functional products such as adhesives,self-adhesives, sealants, foamed products, coatings, powder coatings,thermoplastic elastomers, film compounds, molding compounds, resinmodifiers, coating agents, dampers, semiconductor sealants, water-stopagents, artificial marble and so forth.

BEST MODE FOR CARRYING OUT THE INVENTION

In the following, the present invention is described in further detailwith the examples, but the following examples are by no means limitativeof the scope of the present invention.

EXAMPLES 1 TO 3 AND COMPARATIVE EXAMPLES 1 TO 3

The monomer and halogen compound indicated in Table 1 or 2 were weighedinto a 500 mL autoclave, followed by bubbling for nitrogen purging.Then, under stirring at 100 rpm in a nitrogen gas stream, internalautoclave was kept at 150° C. The polymerization was stopped 16 hoursafter the start of reaction and 5 mL portion of the reaction mixture wassampled, weighed accurately, and concentrated to dryness at 120° C. Theresidue was accurately weighed after drying, and the degree ofpolymerization was calculated. After completion of polymerization, theterminal modifier and solvent B shown in Table 1 or 2 were added in theindicated amounts and the reaction was carried out at 120° C. for 24hours. Thereafter, the unreacted monomer, unreacted terminal modifierand solvent were removed by purification and the polymerization product,designated as A-1 to 3 and F-1 to 3, respectively, was taken out.

EXAMPLES 4, 5 AND 7 AND COMPARATIVE EXAMPLES 4 TO 6

The monomer, radical polymerization initiator, solvent A and halogencompound indicated in Table 1 or 2 were weighed into a 500 mL-volumeseparable flask and a four-neck separable cover, a stirring impeller, athree-way cock, a cooling tube and a temperature probe were attached tothe flask, followed by bubbling for nitrogen purging. Then, understirring at 100 rpm in a nitrogen gas stream, the polymerization wascarried out at an internal temperature of 80° C. The polymerization wasstopped 6 hours after the start of reaction and 5 mL portion of thereaction mixture was sampled, weighed accurately, and concentrated todryness at 120° C. After drying, the residue was weighed accurately andthe degree of polymerization was calculated. After completion ofpolymerization, the terminal modifier shown in Table 1 or 2 was added inthe indicated amount and reacted at 120° C. for 24 hours. Thereafter,the unreacted monomer, unreacted terminal modifier and solvent wereremoved by purification and the polymerization product, designated asB-1, 2, 4 and G-1 to 3, respectively, was taken out.

EXAMPLE 6

2-Ethylhexyl acrylate and the radical polymerization initiator, solventA and halogen compound indicated in Table 1 were weighed into a 500mL-volume separable flask, which was then fitted with a four-neckseparable cover, stirring impeller, three-way cock, cooling tube andtemperature probe, followed by bubbling for nitrogen purging. Then,under stirring at 100 rpm in a nitrogen gas stream, the polymerizationwas carried out at an internal temperature of 80° C. At 6 hours afterthe start of reaction, methyl methacrylate bubbled through with N₂ gasfor nitrogen purging in advance was added as indicated in Table 1. After2 hours, the polymerization was stopped and 5 mL of the reaction mixturewas sampled, weighed accurately, and concentrated to dryness at 120° C.After drying, the residue was weighed accurately and the degree ofpolymerization was calculated. After completion of polymerization, theterminal modifier shown in Table 1 was added in the indicated amount andreacted at120° C. for 24 hours. Thereafter, the unreacted monomer,unreacted terminal modifier and solvent were removed by purification andthe polymerization product B-3 was taken out.

EXAMPLES 8 TO 10 AND 12 AND COMPARATIVE EXAMPLES 7 to 10

The monomer, halogen compound and metal compound indicated in Table 1 or2 were weighed into a 500 mL-volume autoclave followed by bubbling fornitrogen purging. Then, under stirring at 100 rpm in a nitrogen gasstream, the polymerization was carried out at an internal temperature of150° C. The polymerization was stopped 8 hours after the start ofreaction and 5 mL of the reaction mixture was sampled, weighedaccurately, and concentrated to dryness at 120° C. After drying, theresidue was weighed accurately and the degree of polymerization wascalculated. After completion of polymerization, the terminal modifierand solvent B shown in Table 1 or 2 were added in the indicated amountsand the reaction was carried out at 120° C. for 24 hours. Thereafter,the unreacted monomer, unreacted terminal modifier and solvent wereremoved by purification and the polymerization product, designated asC-1 to 3, C-5 and H-1 to 4, respectively, was taken out.

EXAMPLE 11

2-Ethylhexyl acrylate, halogen compound and metal compound indicated inTable 1 were weighed into a 500 mL-volume autoclave, followed bybubbling for nitrogen purging. Then, under stirring at 100 rpm in anitrogen gas stream, the polymerization was carried out at an internaltemperature of 150° C. At 8 hours after the start of reaction, methylmethacrylate bubbled through with N₂ gas for nitrogen purging in advancewas added as indicated in Table 1. After 4 hours, the polymerization wasstopped and 5 mL of the reaction mixture was sampled, weighedaccurately, and concentrated to dryness at 120° C. After drying, theresidue was weighed accurately and the degree of polymerization wascalculated. After completion of polymerization, the terminal modifiershown in Table 1 was added in the indicated amount and reacted at 120° Cfor 24 hours. Thereafter, the unreacted monomer, unreacted terminalmodifier and solvent were removed by purification and the polymerizationproduct C-4 was taken out.

EXAMPLES 13 TO 16 AND COMPARATIVE EXAMPLES 11 TO 14

The monomer and halogen compound indicated in Table 1 or 2 were weighedinto a 500 mL-volume separable flask and a four-neck separable cover, astirring impeller, a three-way cock, a cooling tube and a temperatureprobe were attached to the flask, followed by bubbling for nitrogenpurging. Then, under stirring at 100 rpm in a nitrogen gas stream at aninternal temperature of 65° C., the polymerization by light irradiationwas carried out using a high-pressure mercury vapor lamp (HLR100T-1,product of SEN Light) as the light source. The polymerization wasstopped 5 hours after the start of reaction and 5 mL of the reactionmixture was sampled, weighed accurately, and concentrated to dryness at120° C. After drying, the residue was weighed accurately and the degreeof polymerization was calculated. After completion of polymerization,the terminal modifier and solvent B shown in Table 1 or 2 were added inthe indicated amounts and the reaction was carried out at 120° C. for24hours. Thereafter, the unreacted monomer, unreacted terminal modifierand solvent were removed by purification and the polymerization product,designated as D-1 to 4 and I-1 to 4, respectively, was taken out.

EXAMPLES 17 TO 19 AND 21 AND COMPARATIVE EXAMPLES 15 to 18

The monomer, halogen compound and metal compound indicated in Table 1 or2 were weighed into a 500mL-volume separable flask and a four-neckseparable cover, a stirring impeller, a three-way cock, a cooling tubeand a temperature probe were attached to the flask, followed by bubblingfor nitrogen purging. Then, under stirring at 100 rpm in a nitrogen gasstream at an internal temperature of 65° C., the polymerization by lightirradiation was carried out using a high-pressure mercury vapor lamp(HLR100T-1, product of SEN Light)as the light source. The polymerizationwas stopped 5 hours after the start of reaction and 5 mL of the reactionmixture was sampled, weighed accurately, and concentrated to dryness at120° C. After drying, the residue was weighed accurately and the degreeof polymerization was calculated. After completion of polymerization,the terminal modifier and solvent B shown in Table 1 or 2 were added inthe indicated amounts and the reaction was carried out at 120° C. for 24hours. Thereafter, the unreacted monomer, unreacted terminal modifierand solvent were removed by purification and the polymerization product,designated as E-1 to 3, E-5 and J-1 to 4, respectively, was taken out.

EXAMPLE 20

2-Ethylhexyl acrylate, halogen compound and metal compound indicated inTable 1 were weighed into a 500 mL-volume separable flask and afour-neck separable cover, a stirring impeller, a three-way cock, acooling tube and a temperature probe were attached to the flask,followed by bubbling for nitrogen purging. Then, under stirring at 100rpm in a nitrogen gas stream at an internal temperature of 65° C., thepolymerization by light irradiation was carried out using ahigh-pressure mercury vapor lamp (HLR100T-1, product of SEN Light) asthe light source. At 5 hours after the start of reaction, methylmethacrylate bubbled through gas in advance was added as indicated inTable 1. The polymerization was stopped after 2 hours and 5 mL of thereaction mixture was sampled, weighed accurately, and concentrated todryness at 120° C. After drying, the residue was weighed accurately andthe degree of polymerization was calculated. After completion ofpolymerization, the terminal modifier shown in Table 1 was added in theindicated amount and the reaction was carried out at 120° C. for 24hours. Thereafter, the unreacted monomer, unreacted terminal modifierand solvent were removed by purification and the polymerization product,designated as E-4, was taken out.

TABLE 1 Polymeri- zation Solvent A Monomer initiator Butyl Cyclo-Halogen compound Example 2EHA BA St AN MMA AlBN acetate hexanone IMBBCMB BIMB TIMB  1 100 — — — — — — — 2.2 — — —  2 100 — — — — — — — — —3.6 —  3 — 80 20 — — — — — — — — 5.0  4 100 — — — — 0.8 400 — 2.2 — — — 5 100 — — — — 0.8 400 — — — 3.6 —  6  80 — — — 20 0.8 400 — — — 3.6 — 7 — 80 20 — — 0.8 400 — — — — 5.0  8 100 — — — — — — — 2.2 — — —  9 100— — — — — — — — — 3.6 — 10 — 90 — 10 — — — 100 — 1.8 — — 11  80 — — — 20— 100 — — — 3.6 — 12 — 80 20 — — — 100 — — — — 5.0 13 100 — — — — — — —2.2 — — — 14 100 — — — — — — — — — 3.6 — 15 — 90 — 10 — — — — — 1.8 — —16 — 80 20 — — — — — — — — 5.0 17 100 — — — — — — — 2.2 — — — 18 100 — —— — — — — — — 3.6 — 19 — 90 — 10 — — — 100 — 1.8 — — 20  80 — — — 20 —100 — — — 3.6 — 21 — 80 20 — — — 100 — — — — 5.0 Halogen compoundSolvent B Iodo- Metal compound Butyl Terminal modifier Example IFE DTFADIFH form T2EHA BiOc acetate 2AE APTES AA Polymer  1 — — — — — — 100 2.4— — A-1  2 — — — — — — 100 2.4 — — A-2  3 — — — — — — 100 2.4 — — A-3  4— — — — — — — 2.4 — — B-1  5 — — — — — — — 2.4 — — B-2  6 — — — — — — —— 8.9 — B-3  7 — — — — — — — 2.4 — — B-4  8 — — — — 0.4 — 100 2.4 — —C-1  9 — — — — 0.4 — 100 2.4 — — C-2 10 — — — — — 0.6 — — — 2.3 C-3 11 —— — — — 0.6 — — 8.9 — C-4 12 — — — — 0.4 — — 2.4 — — C-5 13 — — — — — —100 2.4 — — D-1 14 — — — — — — 100 2.4 — — D-2 15 — — — — — — 100 — —2.3 D-3 16 — — — — — — 100 2.4 — — D-4 17 — — — — 0.4 — 100 2.4 — — E-118 — — — — 0.4 — 100 2.4 — — E-2 19 — — — — — 0.6 — — — 2.3 E-3 20 — — —— — 0.6 — — 8.9 — E-4 21 — — — — 0.4 — — 2.4 — — E-5

TABLE 2 Polymeri- zation Solvent A Compar. Monomer initiator ButylCyclo- Halogen compound Example 2EHA BA St AN MMA AlBN acetate hexanoneIMB BCMB BIMB TIMB  1 100 — — — — — — — — — — —  2 100 — — — — — — — — —— —  3 — 80 20 — — — — — — — — —  4 100 — — — — 0.8 400 — — — — —  5 100— — — — 0.8 400 — — — — —  6 — 80 20 — — 0.8 400 — — — — —  7 100 — — —— — — — — — — —  8 100 — — — — — — — — — — —  9 — 90 — 10 — — — — — — —— 10 — 80 20 — — — — — — — — — 11 100 — — — — — — — — — — — 12 100 — — —— — — — — — — — 13 — 90 — 10 — — — — — — — — 14 — 80 20 — — — — — — — —— 15 100 — — — — — — — — — — — 16 100 — — — — — — — — — — — 17 — 90 — 10— — — — — — — — 18 — 80 20 — — — — — — — — — Halogen compound Solvent BIodo- Metal compound Butyl Terminal modifier Example IFE DTFA DIFH formT2EHA BiOc acetate 2AE APTES AA Polymer  1 2.5 — — — — — 100 2.4 — — F-1 2 — — 5.5 — — — 100 2.4 — — F-2  3 — — — 3.9 — — 100 2.4 — — F-3  4 2.5— — — — — — 2.4 — — G-1  5 — — 5.5 — — — — 2.4 — — G-2  6 — — — 3.9 — —— 2.4 — — G-3  7 2.5 — — — 0.4 — 100 2.4 — — H-1  8 — — 5.5 — 0.4 — 1002.4 — — H-2  9 — 2.0 — — — — 100 — — 2.3 H-3 10 — — — 3.9 0.4 — 100 2.4— — H-4 11 2.5 — — — — — 100 2.4 — — I-1 12 — — 5.5 — — — 100 2.4 — —I-2 13 — 2.0 — — — — 100 — — 2.3 I-3 14 — — — 3.9 — — 100 2.4 — — I-4 152.5 — — — — — 100 2.4 — — J-1 16 — — 5.5 — — — 100 2.4 — — J-2 17 — 2.0— — — — 100 — — 2.3 J-3 18 — — — 3.9 — — 100 2.4 — — J-4

The values in Tables 1 and 2 represent parts by weight.

The monomers are indicated by the following abbreviations in Tables 1and 2.

EHA: 2-Ethylhexyl acrylate

BA: Butyl acrylate

St: Styrene

AN: Acrylonitrile

MMA: Methyl methacrylate

The halogen compounds are indicated by the following abbreviations inTables 1 and 2.

IMB: Iodomethylbenzene

BCMB: 1,4-Bis(chloromethyl)benzene

BIMB: 1,4-Bis(iodomethyl)benzene

TIMB: 1,3,5-Tris(iodomethyl)benzene

IFE: Iodoperfluoroethane

DTFA: 1,3-Dichlorotetrafluoroacetone

DIFH: 1,6-Diiodoperfluorohexane

The metal compounds are indicated by the following abbreviations inTables 1 and 2.

T2EHA: Tin bis(2-ethylhexanoate)

BiOc: Bismuth trioctylate

The terminal modifiers are indicated by the following abbreviations inTables 1 and 2.

2AE: 2-Aminoethanol

APTES: 3-Aminopropyltriethoxysilane

AA: Allylamine

Determination of Number Average Molecular Weight and Molecular WeightDistribution

The polymerization product obtained was subjected to gel permeationcolumn chromatography (column: product of Showa Denko: KF-80M×2) usingtetrahydrofuran as the eluent and the number average molecular weight,weight average molecular weight, and molecular weight distribution(MW/MN, the ratio between the weight average molecular weight, MW, andthe number average molecular weight, MN) of the polymerization productwere determined from the calibration curve constructed with polystyrenestandards. The number average molecular weight and molecular weightdistribution (MW/MN) thus obtained are shown in Tables 3 and 4.

Determination of Terminal Functional Group Introduction Rate

Depending on the kind of each terminal group, the following titrimetricprocedure was carried out and the terminal functional group introductionrate was calculated. The terminal functional group introduction rate isexpressed in percentage relative to the number of terminal groupsideally introduced by using the value found from the number of terminalfunctional groups obtained by the titrimetric procedure described belowand the number average molecular weight obtained by gel permeationcolumn chromatography. The terminal functional group introduction ratesthus obtained are shown in Tables 3 and 4.

Assay of the Number of Terminal Hydroxyl Groups

The number of terminal hydroxyl groups in each of the polymerizationproducts obtained in Examples 1 to 5, 7 to 9, 12 to 14, 16 to 18, and 21and Comparative Examples 1 to 8, 10 to 12, 14 to 16, and 18 wascalculated by esterifying with a solution of phthalic anhydride inpyridine and titrating the stoichiometric excess of the reagent with asolution of sodium hydroxide in accordance with JIS K 1557.

Assay of Terminal Vinyl Groups

The number of terminal vinyl groups in each of the polymerizationproducts obtained in Examples 10, 15 and 19 and Comparative Examples 9,13 and 17 was determined by ¹H-NMR in deuteriochloroform and calculated.

Assay of Terminal Ethoxysilyl Groups

The number of terminal ethoxysilyl groups in each of the polymerizationproducts obtained in Examples 6, 11 and 20 was determined by ¹H-NMR indeuteriochloroform and calculated.

TABLE 3 Polymerization Molecular weight Degree of Terminal functionalperiod Number average distribution polymerization group introductionrate Example Polymer (hrs) molecular weight (MW/MN) (%) (%)  1 A-1 16 5000 1.31 48 98  2 A-2 16  5400 1.25 52 96  3 A-3 16  5300 1.32 52 96  4B-1 6 11500  1.64 83 92  5 B-2 6 11000  1.65 94 91  6 B-3 8 10800  1.6592 91  7 B-4 6 12100  1.69 95 90  8 C-1 8 8800 1.44 85 96  9 C-2 8 92001.45 90 97 10 C-3 8 9400 1.47 87 94 11 C-4 12  10100  1.45 91 95 12 C-58 8300 1.47 92 94 13 D-1 5 5200 1.31 50 94 14 D-2 5 4800 1.27 55 97 15D-3 5 5100 1.26 52 97 16 D-4 5 4900 1.29 57 95 17 E-1 5 10400  1.45 9596 18 E-2 5 11000  1.46 96 96 19 E-3 5 10500  1.45 98 97 20 E-4 7 99001.43 95 95 21 E-5 5 10100  1.47 98 94

TABLE 4 Polymerization Molecular weight Degree of Terminal functionalCompar. period Number average distribution polymerization groupintroduction rate Example Polymer (hrs) molecular weight (MW/MN) (%) (%) 1 F-1 16  — — Trace  2 F-2 16  — — Trace —  3 F-3 16  — — Trace —  4G-1 6 19300  2.31 88 68  5 G-2 6 18000  2.20 91 70  6 G-3 6 9600 2.23 9271  7 H-1 8 2500 1.45 15 89  8 H-2 8 4800 1.32 17 81  9 H-3 8 8200 2.3010 67 10 H-4 8 5300 1.38 24 72 11 I-1 5 2900 1.19  4 — 12 I-2 5 31001.18  3 — 13 I-3 5 4800 2.14  2 — 14 I-4 5 3200 1.20  3 — 15 J-1 512500  1.35 39 74 16 J-2 5 14000  1.38 48 68 17 J-3 5 25300  2.23 30 5718 J-4 5 13200  1.82 45 70

INDUSTRIAL APPLICABILITY

In the production method of a functional group-terminated vinyl polymerin accordance with the first and the second aspect of the invention, aradical polymerization is carried out in the presence of a halogencompound having the structure defined hereinabove so that a halogenatom-terminated polymer can be synthesized with certainty. Further, asthe terminal halogen atom is then transformed, the reaction proceedsliving-wise with low chances for side reactions so that a functionalgroup can be easily introduced into the terminus to produce theobjective polymer practically without reaction condition problems suchas strictly anhydrous conditions.

Furthermore, using a 14 to 16 metal compound in the step of said radicalpolymerization leads to a curtailed reaction period and a higher degreeof polymerization of the vinyl polymer.

In addition, the functional group-terminated vinyl polymer according tothe third aspect of the invention has a number average molecular weightwithin a defined range and the chain extension by terminal-terminalcrosslinking takes place with good efficiency so that a high molecularweight polymer having a linearly elongated chain can be produced and,therefore, a cured product with good elongation and tensile strength,outstanding heat resistance, water resistance and durability can beobtained.

Therefore, the functional group-terminated vinyl polymer according tothe third aspect of the invention is useful as a raw material for theproduction of various functional products.

What is claimed is:
 1. A production method of a functionalgroup-terminated vinyl polymer comprising a step of synthesizing ahalogen atom-terminated vinyl polymer by the radical polymerizationreaction of a vinyl monomer in the presence of a halogen compound and astep of introducing a functional group to a terminus by substituting afunctional group-containing group for the terminal halogen atom of saidvinyl polymer, said halogen compound having a structure such that saidhalogen atom is bound to a carbon atom linked to an aromatic ring andsaid radical polymerization reaction being carried out either by lightirradiation or light irradiation in the presence of a Group 14 to 16metal compound or by heating in the presence of a Group 14 to 16 metalcompound.
 2. A production method of a functional group-terminated vinylpolymer comprising a step of synthesizing an iodine atom-terminatedvinyl polymer by the radical polymerization reaction of a vinyl monomerin the presence of an iodine compound and a step of introducing afunctional group to the terminus by substituting a functionalgroup-containing group for the terminal iodine atom of said vinylpolymer, said iodine compound having a structure such that said iodineatom is bound to a carbon atom linked to an aromatic ring and saidradical polymerization reaction being carried out either by heating orby heating in the presence of a radical polymerization initiator.
 3. Theproduction method of a functional group-terminated vinyl polymeraccording to claim 2, wherein the iodine compound has two or more iodineatoms.
 4. The production method of a functional group-terminated vinylpolymer according to claim 2, wherein the functional group to beintroduced into a terminus is one or more fustian groups selected fromthe group consisting of hydroxyl, amino, carboxyl, vinyl and silylgroups.
 5. A production method of a functional group-terminated vinylpolymer comprising a step of synthesizing a halogen atom-terminatedvinyl polymer by the radical polymerization reaction of vinyl monomer inthe presence of a halogen compound and a step of introducing afunctional group to a terminus by substituting a functionalgroup-containing group for the terminal halogen atom of said vinylpolymer, said halogen compound having a structure such that said halogenatom is bound to a carbon atom linked to an aromatic ring and saidradical polymerization reaction being carried out either by lightirradiation in the presence of a tin compound or a bismuth compound orby heating in the presence of a tin compound or a bismuth compound. 6.The production method of a functional group-terminated vinyl polymeraccording to claim 1, wherein the halogen compound has two or morehalogen atoms.
 7. The production method of a functional group-terminatedvinyl polymer according to claim 1, wherein the functional group to beintroduced into a terminus is one or more functional groups selectedfrom the group consisting of hydroxyl, amino, carboxyl, vinyl and silylgroups.
 8. The production method of a functional group-terminated vinylpolymer according to claim 3, wherein the functional group to beintroduced into a terminus is one or more functional groups selectedfrom the group consisting of hydroxy, amino, carboxyl, vinyl and silylgroups.
 9. The production method of a functional group-terminated vinylpolymer according to claim 5, wherein the halogen compound has two ormore halogen atoms.
 10. The production method of a functionalgroup-terminated vinyl polymer according to claim 5, wherein thefunctional group to be introduced into a terminus is one or morefunctional groups selected from the group consisting of hydroxyl, amino,carboxyl, vinyl and silyl groups.
 11. The production method of afunctional group-terminated vinyl polymer according to claim 6, whereinthe functional group to be introduced into a terminus is one or morefunctional groups selected from the group consisting of hydroxyl, amino,carboxyl, vinyl and silyl groups.